Anthraquinone derivatives



Patented May 21, 1935 UNITED'STATES PATENT OFFICE" ANTHRAQUINONE DERIVATIVES Ralph Norbeit Lulek, Wilmington, Del., assignor I to E. I. du Pont de Ncmours & Company, Wil- -mington, Del., a corporation of Delaware No Drawing.

9'Claims. This invention relates to carbon compounds and methods for their production. More particularly it relates to derivatives of l-aminoanthraqu'inone-G-carboxylic acid. It especially contemplates the dyes and v dye intermediates produced by the condensation of l-aminoanthraquinone-G-carboxylic acid with other chemical compounds.

It has been shown by Eckert (Monatshefts iiir Chemie 35, 289, 1914) that by nitrating anthraquinone-b-aldehyde, oxidizing the resulting nitroanthraquinone-aldehyde, and reducing it to the amino-carboxylic acid of anthraquinone, that the compound produced is l-amino-anthraquinone- G-carboxylic'acid. So far as is known this material has never been used in the production of vat colors or intermediates therefor.

This invention has for an object the production of new and valuable chemical compounds. Other objects are to produce dye intermediates of a novel type, to produce new vat colors, to

produce new dyes, to devise processes for the manufacture of new anthraquinone. derivatives and in general to advance the art. Other objects will appear hereinafter.

' These objects are accomplished by the present invention whereby l-amino-anthraquinone-G- carboxylic acid is condensed with carbonyl halides, presumably according to the equation:

the resultant carboxylic acids changed to the cor- Application August 18, 1931, Serial No. 557,955

responding carbonyl chlorides, presumably acand the resultant acid chlorides thereafter condensed with amines, presumably according to the equation:

U 0 In the general process of this invention as set out in the precedingequations and. formulae, R and Q represent carbon compound radicals or nuclei. The invention will be further understood from a consideration of the following examples in which the proportions are given by weight.

PART ICONDENSATION WITH CARBONYL HALIDES Example I Ten (10) parts of lamino-anthraquinone-6- carboxylic acid are heated and stirred with 11.8 parts of 1,9-anthraisothiazole-2-carbonyl-chloride in 300 parts nitrobenzene to C. 'for one hour. The new condensation product separates out in yellow needles and may be filtered off after cooling the charge.

The reaction involved is Example II Ten-(l) parts of l-amino-anthraquinone-B- carboxylic acid are heated and stirred with 13 parts of 1,9-anthraiso-selenazole-2-carbonylchloride in 300 parts nitrobenzene to 150 C. for one hour. The new condensation product separates out in yellow needles and may be filtered oil after cooling the charge. The reaction involved is represented by the following probable equation:

1 Example III Ten (10) parts of 1amino-anthraquinorie-G carboxylic acid were reacted with 7.5 parts of beta-naphthoyl-chloride in 70 parts of ortho-dichloro-benzene by heating at 125-145" C. for 1-2 Ten (10) parts of l-amino-anthraquinone-G- carboxylic acid were reacted with 8 parts of metamethoxy-benzoyl-chloride in 100 parts of xylene While heating at 130-150 C. for 1-2 hours. The reaction taking place is represented by the following probable equation:

o o H t n u 1 i V o-on II o EmampleV 'Ten (10) parts of l-amimi-anthraquinonia-S- carboxylic acid and 8.8 parts of tere-phthaloylchloride were caused to react by heating together in 80 parts of nitrobenzene at Mil-150 C. for l-2 hours. The product which formed was separated, suitably purified.- and dried. The reaction taking hOuTSi The su t Compound Was isolated, place is represented by the following probable washed and dried. The reaction taking place is equation:

-0 0 H41? 1 V 0 ll WL JLC. Hort o Ig- BIO-(If I represented by the following probable equation: 7

o H -II I or A 51 0 o11 O-OH Y" Example VI Ten (10) parts of 1-amino-anthraquinone-6- carboxylic acid-were suspended in 50-80 parts of i 5 nitrobenzene and '7 parts of benzoyl-chloride added. The solution was heated to 120-130 C.

n 0o1 HN 0 and the temperaturemaintained at this point for one hour. The mass was then cooled, filtered and washed. The reaction involved is represented by the following probable equation:

Ten (10) parts of' l-amino-anthraquinone-ficarboxylic acid and 10.2 parts of anthraquinone- Z-carbonyl-chloride were condensed at 150 C. in parts of nitrobenzene. A product giving a yellow sulphuric acid solution and a wine colored alkaline hydrosulphite vat was produced. The reaction taking place is illustrated by the following probable equation:

This new produot after being vatted and applied to the fiber oxidized through green'and brown to alightyellow. Example VIII -..Te'n;'( 10) parts of l-amino-anthraquinone-G- carboxylic acid were heated together with 14.5 parts of anthraquinone-2 l-phenyl-acridone-l carbonyl-chloride in 100 parts of nitrobenzene to -130 C. The reaction was finished after. about one-half hour. The mass' was cooled to 80 C., filtered, washed and dried. The reaction taking place-is represented by the following probable equation:

PART IICONVEllSION 1'0 CARBONYL HALIDES Example IX The wet cake from Example l was suspended I in 100 parts of nitrobenzene, 16 parts of phosrepresented by the following probable equation:

C-Cl

Example X The wet cake from Example II was suspended in 100 parts nitrobenzene, 16 parts of phosphorus pentachloride added, the mass heated at 100 C.

for one hour and afterwards cooled. When cooled the acid chloride was filtered, washed with nitrobenzene and benzene and'dried. Theresultant product was a dark yellow crystalline powder soluble in concentrated sulphuric acid and pyridine with a yellow color. The reaction taking place was represented by the following I probable equation:

Example XI The filter cake resulting from Example VI was suspended in parts of nitrobenzene and thereafter 10'parts of phosphorus pentachloride added.

The mixture was heated to 100 C. and maintained at that temperature for one-half hour. The resultant product was filtered at room temperature, Washed and dried. The reaction taking place is represented by the following probable equation:

II I (J-N o o I I I you If H I v g 0 a Example XII The resultant product from the process of Ex- HaCO 'I; q I I too (I II ample VIII was suspended in 40-50 parts of nitrobenzene and 10 parts of phosphorus pentachloride added. The suspension was heated to 80 C'. When the reaction was complete the resultant acid chloride was isolated by filtration. The reaction taking place is represented by the following probable equation:

PART IIICONDENSATION WITH AMINEs Example XIII Ten (10) parts of l-meta-methoxy-benzoylamino-anthraquinone-G-carbonyl chloride (Ex. IV) were condensed with 5.3 parts of alphaamino-anthraquinone by heating in 125 parts of nitrobenzene at 140 C. for 2 hours. The reaction taking place is represented by the following probable equation:

Example XI V Ten (10) parts of l-benzoyl-amino-anthraquinone-6-carbonyl-chloride (Exs. VI and XI) were heated with 5.7 parts of alpha-amino-anthraquinone in 150 parts of nitrobenzene to 130-140" C. and this temperature maintained for about one hour. The mass was then cooled to 60-70 C. and filtered/washed and dried. It is a yellowish powder, soluble in sulphuric acid with a yellow color and dyes cotton in yellowish shades. The reaction taking place is represented by the following probable equation:

example xv I Ten (10) parts of 1-benzoyl-amino-anthraquinone-G-carbonyl-chloride (Exs. VI and XI) were suspended in 200 parts of nitrobenzene and 6.6 parts of 1-amino-fi-chloro-anthraquinone added. The suspension was heated to, 140-450 C. and maintained at this temperature for one hour. The resultant mass was then cooled to C., filtered,'wa.shed and dried. The resultant prodnot l is a yellow powder soluble in sulphuric acid with a yellow color and dyes cotton inxyellow shades of extreme fastness. The reaction taking place is represented by the following equation:

Ten (10) parts of benzoyl-amino-l-anthraquinone-6-carbonyl-chloride (Exs. VI and XI) were reacted with 1.4 parts of para-phenylene-diamine in parts of nitrobenzene while the temperature was maintained tattabout 150 C. The

reaction taking place is illustrated by the following probable equation:

Example XVII Ten- (10) parts of benzoyl-amino-anthra-f quinone-fi-carbonyl-chloride (Exs.VI and XI) and 2.36 parts of benzidine were caused to react by heating together in 150-200 parts of nitrobenzene at -150" C. fort2r hours. The reaction taking.

probable place is represented by the following probable equation? a reaction taking place is'represented by the following probable equation:

' Ihe resultant product was isolated and dried. It gives a yellow to orange color in' sulphuric acid and a red' colored alkaline hydrosulphite vat.

orange to yellow-brown to yellow shades.

IN 0 I A V v 0-01 I i i I n I I v I o The leuco compound oxidizes on cotton through Example XIX Ten (10) parts of l-beta-anthraquinoyl-am- II -o H u I' QN O n I if? 0 H I Y W O O H ino-anthraquinone-G-carbonyl-chloride (EX.VII) and. 4.3 parts of alpha-amino-anthraquinone were caused to condense by heating together in L59 parts of nitrobenzene' at 150 C. for 2 hours. The. reaction-taking place is represented by the fol-l lowing probable equation:

. Example XX 'Ten (10) parts of 1',9'-anthraisothiazoyl-1- an'lino anthraquinone-fi-carbonyl-chloride (Exs. I and IX) Were heatedwith 4.5 parts of alpha-amino-anthraquinone in 250 parts of nitrobenzene at l50-l60 Cjfor about one hour. The resultant yellow crystalline mass was cooled to 70 C. and

filtered. "The product was thereafter washed withnitrobenzene and alcohol anddried. The product dissolves in sulphuric acid with a yellowish-orange color and dyes from a reddish- Example XXII In 250 parts of nitrobenzene there was suspended 10 parts of l,9-anthraisotl'1iazoyl-1-amino-anthraquinone-fi-carbonyl-chloride (Exs. I

gi g i ggfiggg igg 'gsf g ggf and IX) and 6.2 parts of mono-benzoyl-LS-di-amble 5 3 2; ep y p g p 7 ino-anthraquinone and the resultant suspension q i heated to 150? C. for a period of one and one-half Y I A if a I a -ofN .0 H-N o NS II- II II i 0 y L 1; 0 II 15 y E Y 20 Example XXI A suspension of 10 parts of l 9-anthraiso- V 5 thiazoyl-l-amino-anthraquinone-6-carbonylhours. The product which consisted of yellow chloride (Exs. I and IX) and 4.7 parts of l-aminoneedles separated out and was filtered at 80-90" 6-chloroanthraquinone in 300 parts of nitroben- Cl, washed with nitrobn'zene and alcohol, and zene was heated to 140-150" C. until no undried. It dissolves in concentrated sulphuric acid changed starting material remained. After 0001- with yellow to orange color and dyes cotton from 30 ing to about 80 C. the resultant dyestuff was a blue vat in fast yellow shades. The reaction filtered off, washed with nitrobenzene and beninvolved is disclosed by the following probable zene and dried. It dissolves with a yellow color equation: 5 V

F H I f 0 0 Y 7+ 40 0 fi-Ol I O l o I o N("J II 0 H H I O--N in sulphuric acid and dyes cotton in yellowish shades. The reaction involved is represented by the following probable equation:

" l i i r a.

CN o HN (i 1 I-s as A -o-o1 01 Y t Y Y 4 0 0 i 0 Example XXIII I'en (10).parts of l';9'-anthraisothiazoyl'-1- hydrosulphite vat. The reaction taking place is probably represented by the following equation:

NS t t? I II H ,9 H 11 o if 0 0-01 HN ll O c) r w v 0 I I C-N 115 e n I ll 0 H O amino-anthraquinone-S-carb'onyl-chloride (Exs. I and IX) was suspended in 260 parts of aniline and heated at 135-150" C. for one hour. The reaction mixture was cooled, filtered and washed with aniline, dilute hydrochloric acid and water in the order named. A dyestufi was produced which was yellow to orange in color when dissolved in sulphuric acid and which dyed cotton in greenish-yellow shades from a blue alkaline hydrosulphite vat. The reaction taking place is probably represented by the following equation:

n v i O I Example XXIV cotton in greenish-yellow shades from a blue A k I if Example XXV Ten parts of 1',9'-anthraisothiazoyl-1 aminoanthraquinone-6-carbonyl-chloride (Exs. I and IX) and 3 parts of para-anisidine were heated together in 150 parts of nitrobenzene at 140-150" C. for one. to two hours. The reaction mixture was ccoled,filtered and washed with-nitrobenzene and alcohol. The reaction taking place is represented by the following probable equation: 7

O-CH3 H III C--N O OCHa 0 WT I O H O H II C 0 tr 0 H The resultant product gives a yellow sulphuric acid solution and dyes cotton in a greenish-yellow shade from a blue hydrosulphite vat.

Example XXVI Ten (10) parts of l-beta-naphthoyl-aminoanthraquinone-S-carbonyl-chloride (EX. III) and 5.1 parts of alphaamino-anthraquinone were caused to react by heating together in 120 parts of nitrobenzene at 140 C. for 1-2 hours. The

enem follow ,Ten (10) parts of the acid chloride obtained reaction taking place is illustratedby the ing probable equation:

I! C N 0 Example XXVII Ten (10) parts of the acid chloride obtained according to Examples VIII and XII, were heated together with 3.4 parts of alpha-amino-anthraquinone in 150 parts of nitrobenzene to 140-150 C. The temperature was maintained 'for one hour after which the mass was cooled. to -80 C. and filtered. The, resultant product is an orange powder which dissolves in sulphuricacid" Example ,XXVIII according toExample's VIII and XII, weresuspended in 150 parts of nitrobenzene and 3.9 parts of l-amino-6-chloro-anthraquinone added. The temperature was raised to -140 C. The condensation product separated out in the formof yellow-orange crystals and was filtered at 70-80 C. It dyes cotton in yellow-orange shades from a Bordeaux vat. The reaction taking place is represented by the following probable equation:

to a yellow color and dyes cotton in orange (LN 2 M,- 9

shades. The reaction taking place is represented by the following probable equation:

Example XXX Ten (10) parts of anthraqu'inQne-Z :l-phenylacridone-4-carbonylamino-anthraquinone-G' carbonyl-chloride (Exs. VIII and XII) were suspended in 200 parts of. aniline and heated at 135150 C. for one hour.

resultant product was a dyestuff which produces a yellow to orange color in sulphuric acid and which dyes cotton an orange shade from a redviolet-color-alkaline hydrosulphite vat. The reaction taking place is represented by the following probable equation:

It is to be understood that the invention is not limited to the condensation of the particular compounds-set out in the above examples. In the general formula, R'and Q may represent any organic radical or residue. For the condensation with the amino group of the l-amino-anthraquinone-G-carboxylic acid, there may be used satisfactorily such compounds as acetyl chloride, succinyl chloride, chloracetic acid chloride,

The reaction mass was, cooled, filtered washed, respectively, with aniline, dilute hydrochloric acid and water. The

prd inyi chloride,

chloride oxalyl chloride, benzoyl meta-anisyl chloride para-nitro-benzoyl chloride C-Cl para-chloro-benzoyl chloride (Iii-Cl O 'tererphthaloyl-chloride alpha-naphthoyl-chloride beta-naphthoyl chloride (l-Cl O beta-anthraqulnone-cerbonyl-chlorlde 1 9-anthraiBothiazo1e-4-carbonyl-chlorlde 1 ll-anthraisothlophene-zearbonylvchlorldo anthnquinona-Z l-phenylmcrjldone-f-mrbonyl-chlorldo For the condensation with the acid chloride group of the l-amino anthraqulnone-fi-carbonylchloride, desirable results an produced with such compounds as ethyl ammeymethyl amine, aniline dl-phenyl amine para-phenylene-dlmmine NH: beta-naphthylexnlne elpha-naphthylem in;

v benzldine n r n It is desired to emphasize the fact that the above examples and list of specific'compounds are merely given as outstanding examples and in no way limit the invention. So far as now appears any amine or carbonyl halide may be used in the condensations set out. While carbonyl-chlorides have been used in the specification to illustrate the invention, it is to be understood that carbonyl halides in general, may be utilized. v

In the course of the specification certain equations and formulaehave been given forthe purpose of aiding in understanding the invention and it is to be understood that it is not desired to limit the invention thereby.

As will be clear from the examples the solvent (if any) used may be varied over a wide range depending upon the characteristics of the particular condensation being carried out. The particular temperatures and time utilized for the various condensations depend upon the physical characteristics of the substances being condensed. The solvent, temperature, time and other mechanical features of the invention which are most desirable for any particular reaction may be readily determined by one skilled in the art. Any desired agent may be used for the conversion to the carbonyl halide.

. Throughout the specification and claims the term vat color is used to cover compounds susceptible to vatting by any of the well known methods.

By this invention an entire new field of anthraquinone vat dyestuffs is opened. The compounds produced have very desirable properties. While the shade of the dyestufis produced varies with the particular formulae in general, the colors fall Within the range of orange, yellow and brown.

As many apparently widely different embodiments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that I do not limit myself to the specific embodiments thereof except by the appended claims.

I claim:

1. A chemical compound having the probable formula Eli o in which R. represents the nucleus of a carbon compound and Q represents the nucleus of a carbon compound.

2. The process which comprises condensing l-amino-anthraquinone-S-carboxylic acid with the carbonyl-halide of a carbon compound, converting the resultant to the corresponding anthraquinone-G-carbonyl-halide and condensins said last mentioned compound with an amino carbon compound.

3. The dyestuff having the probable formula 4. The process which comprises condensing 1-amino-anthraquinone-fi-carboxylic-acid with 1 9-anthraisothiazole-2-carbonyl-chloride, converting the resultant carboxylic acid to a carbonyl-halide and condensing it with l-amino-6- chloro-anthraquinone.

5. A chemical compound which has the formula and in which Q represents the nucleus of a carbon compound.

6. A chemical compound which has the formula '7. A chemical compound which has the formula (|2--NH-anthraqulnone radical and in which R. represents the nucleus of a carbon compound.

8. A chemical compound which has the formula,

14- 2,001,737 7 9. The chemical compound probably having in which R represents thenuc leus, radical or the formula V residue of a carbon compound and which results v I O V a from condensing the carbonyl halide of a carbon 5 1 compound with 1-aminoranthraquinone-6-car- X 7 corresponding carbonyl halide and condensing f the last mentioned carbonyl halide with an 0,-Smine radical amine.

' RALPH N. LULEK.

| boxylic acid, converting the resultant acid to the Certificate of Correction Patent No. 2,001,737. May 21, 1935.

RALPH NORBEIT LULEK It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 5, lines 30 to 40, Example XIV, strike out the extreme right hand portion of the formula and insert insteadu l C-N O O u C-N O n I n O and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 20th day of August, A. D. 1935 [SEAL] LESLIE FRAZER,

Acting Commissioner of Patents. 

